Hydrocarbon catalysis process



Patented July 2.2, 1941 I HYDROCARBON CATALYSIS PROCESS I Robert E. Burkand Everett 0. Hughes, Cleveland Heights, Ohio, assignors to TheStandard Oil Company, Cleveland, Ohio, a corporation of Ohio No Drawing.Original application September 1,

1938, Serial No. 228,005.

Divided and this application December 9, 1939, SerialNo. 308,446

. 16 Claims.

This invention relates to catalysis, and more particularly catalysisinvolving operation on hydrocarbons; and it is among the objects of theinvention to provide improved operating efa be employed.

The raw material applicable for reaction may be non-benzenoidhydrocarbons, or fractions containing them, etc., and it is subjected tothe action of a compound catalyst of peculiar character, and heat. vInour work in oxide catalytic agents we have found that a combination ofelements described hereinafter gives surprising results, and which areout of relation to the behavior of the individual components or othercombinations. This catalyst may be prepared preferably from solublesalts of tin, aluminum and chromium for example by dissolving the saltsin water at the rate of two mol per cent of tin, seventy-eight mol percent of aluminum and twenty mol per cent of chromium, and the solutionis treated with ammonia to neutralization. Thus, tin chloride andaluminum'nitrate and chromium nitrate at the rate of 78.2, 2500, and 713g. respectively, based on anhydrous salts, per 18.8 liters of distilledwater, beingbrought into solution, the solution is warmed to about 55C., and being introduced into a container provided with an agitator,concentrated ammonium hydroxide 2310 g. and 1500 g. ammonium'acet'ateper 11.2 liters of distilled water issupplied. A

blue-green precipitate is formed which'is allowed.

to settle for about two hours, and the cake resulting is washed threetimes-by dispersion into four liters of water, and is filtered. Theprecipi-f tate is dried at about 140 F., and then under vacuum at about400 F. A vitreous gel results.

The proportions of tin and aluminum and chromium are most desirablythose as above-inr dicated, but in general the tin need not advisably beless than one or more than thirty mol per cent and the aluminum not lessthan fifty nor more than ninety mol per cent, the remainder beingchromium. In some instances antimony may replace all or part of the tin.Again in some instances beryllium may replace all or part of thealuminum. That is, an element from the group of laterally adjacentatomic numbers 50 and 51 in theperiodic table and an amphoteric oxideforming element from the diagonally adjacent atomic numbers 4 and 13 inthe periodic table and chromium may be combined. Thus, antimony chlorideand aluminum nitrate and chromium nitrate at the rate of 68.4, 2500 and713 g. respectively per 18.8 liters of distilled water, being broughtinto solution, the solution is warmed and with vigorous agitationammonium-hydroxide is introduced at the rate of 2310 g. of concentratedammonium hydroxide with 1500 g. of ammonium acetate per 112 liters ofdistilled water. Again similarly, SnClr and Be(NOa)2 and CI(NO3)3 may bedissolved at the rate of 78.2, 1550 and 713 g. respectively per 18.8liters of distilled water, and the solution being warmed and agitatedammonium hydroxide is'introduced at the rate of 1820 g. of concentrated(28%) ammonium hydroxide and ammonium actate 1500 g. in 11.2 liters ofdistilled water.

Where a part of the tin or aluminum is replaced by antimony or berylliumrespectivelmthe catalyst involves tin and antimony and aluminum andchromium, or beryllium and aluminum andtin and chromium, or berylliumand aluminum and tin and antimony and chromium, etc., on the lines asindicated and within the-proportions stated for the permissible rangesof the tin and aluminum components, the generic properties of thecatalystbeing maintained.

The compound catalyst is suitably granulated to provide interstitialspaces for passage of the material to be treated, in adequate contact,and is arranged in a reaction zone with adequate heating means, suchthat the temperature of the mass may be maintained around 500 C. mostdesirably, or at least in general not under about 375 or over about 6750., the raw material beingpassed into contact with the catalyst. Thepressure may be atmospheric to not in excess of about two hundred poundsper square inch, preferably a nominal pressure. The raw material, forillustration hydrocarbons normally gaseous such as ethane to pentane,pure hydrocarbons such as n-hexane, n-heptane, n-octane, etc., naphthasor' .distillates from stocks which are predominantly non-benzenoid, asfor instance derived from, Pennsylvania, Michigan; Kentucky, Ohio, Mid-Continent and the like petroleum, (for example Pennsylvania or Michigannaphthas in boiling range to 215 0.) naphthenic naphthaetc. is thusbrought into contact with, the catalyst, and

may be re-passed in whole or part, wherede- 'sired. The aromatics and/orunsaturates in the products passing from the treating zone may beseparated, e. g. by mixing with a solvent having the selective characterof sulphur dioxide, or a high boiling amine, 0.75-3 or somewhat morevolumes being employed, and the portion of the products not dissolved bythe solvent may, on separation, be re-passed through the catalytic zone.

This application is a division of our application Ser. No. 228,005,filed Sept. 1, 1938.

Other modes of applying the principle of the invention may be employed,change being made as regards the details described, provided thefeatures stated in any of the following claims, or the equivalent ofsuch, be employed.

We therefore particularly point out and distinctly claim as ourinvention:

1. In a process of aromatizing hydrocarbons, subjecting a naphthacontaining non-benzenoid hydrocarbons to a temperature of 375-675 C. andthe action of an oxide contact-mass formed from co-precipitation from asolution of tin chloride and aluminum nitrate and chromium nitrate inproportions of substantially 2 and 78 and 20 moi per cent of tin,aluminum and chromium respectively.

2. In a process of aromatizing hydrocarbons, subjecting a naphthacontaining non-benzenoid hydrocarbons to a temperature of 375-675" C.and the action of an oxide contact-mass formed from co-precipitationfrom dissolved salts of tin and aluminum and chromium, the tin in thecontact mass being 1-30 mol per cent.

3. In a process of 'aromatizing hydrocarbons, subjecting a naphthacontaining non-benzenoid hydrocarbons to a temperature of 375-675 C. andthe action of an oxide contact-mass formed from co-precipitation fromdissolved salts of antimony and aluminum and chromium, the antimony inthe contact-mass being 1-30 mol per cent.

4. In a process of aromatizing hydrocarbons, subjecting a naphthacontaining non-benzenoid hydrocarbons to a temperature-of 3'75-675 C.and the action of an oxide contact-mass formed from co-precipitationfrom dissolved salts of tin and beryllium and chromium, the tin in thecon tact-mass being 1-30 mol per cent.

5. In a process of aromatizing hydrocarbons, subjecting a naphthacontaining non-benzenoid hydrocarbons to a temperature of 3'75-6'75 C.and the action of an oxide contact-mass formed from co-precipitationfrom dissolved salts of chromium and an amphoteric oxide forming elementfrom the group consisting of beryllium and aluminum, and an acid oxideforming element from the group consisting of tin and antimony,

7. In a processof the character described, subjecting a non-benzenoidhydrocarbon to 'a temperature of 375-675 C. and the action of an oxidecontact-mass formed from co-precipitation from dissolved salts 0! tinand aluminum and chromium, the tin in the contact mass being 1-30 molper cent.

8. In a process of the character described, subjecting a non-benzenoidhydrocarbon to a temperature 01 375-675 C. and the action oi an oxidecontact-mass formed from co-precipitation from dissolved salts orantimony and aluminum such amphoteric oxide forming element and acidoxide forming element in the contactmass being 50-90 mol per cent and1-30 mol per cent respectively.

6. In a process of the character described, subjecting a non-benzenoidhydrocarbon to a temperature of 375-675" C. and the action of an oxidecontact-mass formed from co-precipitation from a solution of tinchloride and aluminum nitrate and chromium nitrate in proportions ofsubstantially 2 and 78 and 20 mol per cent of tin, aluminum and chromiumrespectively.

and chromium, the antimony in the contactmass being 1-30 per cent.

9. In a process of the character described, subjecting a non-benzenoidhydrocarbon to a temperature of 375-675 C. and the action of an oxidecontact-mass formed from co-precipitation from dissolved salts of tinand beryllium and chromium, the tin in the contact-mass being 1-30 molper cent.

10. In a process oi the character described, subjecting a non-benzenoidhydrocarbon to a temperature of 375-675 C. and the .action of an oxidecontact-mass formed from co-precipitation from dissolved salts ofchromium and an amphoteric oxide forming element from the groupconsisting of beryllium and aluminum, and an acid oxide forming elementfrom the group consisting of tin and antimony, such amphoteric oxideforming element and acid oxide forming element in the contact-mass being50-90 mol per cent and 1-30 mol per cent respectively.

11. In a process of the character described, at a temperature of 375-675C. passing a nonbenzenoid naphtha into contact at a rate of about oneliter per hour per liter of catalyst with an oxide catalyst formed fromco-precipitation from dissolved salts of antimony and aluminum andchromium, the antimony in the contact-mass being 1-30 mol per cent.

12. In a process of the character described, at a temperature of3'75-6'75 C. passing a non-benzenoid naphtha into contact at a rate ofabout one liter per hour per liter of catalyst with an oxide catalystformed from co-precipitation from dissolved salts of tin and berylliumand chromium, the tin in the contact-mass being 1-30 mol per cent.

13. In a process of the character described, at a temperature of 375-675C. passing a non-benzenoid naphtha into contact at a rate of about oneliter per hour per liter of catalyst with an oxide catalyst formed fromco-precipitation from dissolved salts of chromium and an amphotericoxide forming element from the group consisting ofberyllium andaluminum, and an acid oxide forming element from the group consistingoi. tin and antimony, such amphoteric oxide forming element and acidoxide forming element in the contact-massbeing 50-90 mol per cent and1-30 moi per centrespectively.

14. In a process of the character described, subjecting a non-benzenoidhydrocarbon to a temperature of 375-675 C. and the action of an oxidecontact-mass formed from co-precipitation from dissolved salts ofantimony and aluminum and chromium, the antimony in the contact-massbeing 1-30 mol per cent, separating aromatics from the product, andreturning the non-aromatic portion of the product to the contact-mass.

' 15. In a process of the character described, subjecting anon-benzenoid hydrocarbon to a temperature of 375-675 C. and the actionof an oxide contact-mass formed from co-precipitation from dissolvedsalts of tin and beryllium and chromium, the tinin the contact-massbeing 1-30 mol per cent, separating -aromatics from the product. andreturning the non-aromatic portion of the product to the contact-mass.

16. In a process 01' the character described, I

subjecting a non-benzenoid hydrocarbon to, a

7 temperature of 375-6'75 C. and the action of an oxide contact-massformed from co-precipitation 10 from dissolved salts of chromium and anamphoteric oxide forming element from the group 'conin the contact-massbeing 50-90 mol per cent and "1-30 mol per cent respectively, separatingaromatics from the product, and returning the non- '-aromatic portion ofthe product to the contact mass. g y 4 ROBERT E. BURK.

C. HUGHES.

